JP6768088B2 - Etching method of electrode foil for low-voltage aluminum electrolytic capacitors with low contact resistance - Google Patents
Etching method of electrode foil for low-voltage aluminum electrolytic capacitors with low contact resistance Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
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Description
本発明は、コンデンサ用の低圧用陽極箔の電気化学エッチング方法に関する。 The present invention relates to an electrochemical etching method for a low voltage anode foil for a capacitor.
現在、アルミニウム電解コンデンサ用の低圧用エッチング箔の周波数変換エッチング方法は、（1）酸液前処理、（2）穴あけエッチング、（3）穴を拡げるエッチング；（4）後処理、洗浄及びアニールである。エッチング中に用いられる電源周波数は商用周波数（５０Ｈｚ）であり、エッチング後、残芯層の厚さが不均一であり、エッチング層のエッチング量が大きく、エッチングされたアルミニウム粉が十分に洗浄されないので、化成後の電極箔の接触抵抗が大きくなってしまう。それ以外に、洗浄効果が好ましくなく、不純物イオンを残留し、電極箔漏電流及びアルミニウム電解コンデンサの使用年数に影響することにもなってしまう。 Currently, the frequency conversion etching methods for low-voltage etching foils for aluminum electrolytic capacitors are (1) acid solution pretreatment, (2) drilling etching, (3) hole expansion etching; (4) posttreatment, cleaning and annealing. is there. The power frequency used during etching is a commercial frequency (50 Hz), and after etching, the thickness of the residual core layer is non-uniform, the etching amount of the etching layer is large, and the etched aluminum powder is not sufficiently washed. , The contact resistance of the electrode foil after chemical conversion becomes large. In addition, the cleaning effect is not preferable, and impurity ions remain, which affects the electrode foil leakage current and the years of use of the aluminum electrolytic capacitor.
本発明の目的は、以上の課題を克服するために、洗浄効果が良く、不純物イオンが少なく、接触抵抗が低く、使用年数が長いコンデンサ用の低圧用陽極箔の電気化学エッチング方法を提供することにある。 An object of the present invention is to provide an electrochemical etching method for a low-voltage anode foil for a capacitor having a good cleaning effect, a small amount of impurity ions, a low contact resistance, and a long service life in order to overcome the above problems. It is in.
本発明の目的は、
（ａ）０．０１〜５ｗｔ％の水酸化ナトリウム溶液で、２０〜６０℃温度で電解コンデンサ用の低圧用陽極箔を０．５〜３分間浸漬する工程と、
（ｂ）工程（ａ）で得られる陽極箔を６〜１２ｗｔ％塩酸、０．０５〜１ｗｔ％硫酸で、温度が５〜５０℃であり、電流密度が０．１〜１Ａ／ｃｍ2である条件で１０〜８５秒処理する工程と、
（ｃ）工程（ｂ）で得られる陽極箔を６〜１２ｗｔ％塩酸、０．０５〜１ｗｔ％硫酸で、温度が５〜５０℃である条件で１０〜８５秒処理する工程と、
（ｄ）工程（ｃ）で得られる陽極箔を温度が４０〜６０℃の水道水で１０〜８５秒洗浄する工程と、
（ｅ）工程（ｂ）、（ｃ、）（ｄ）を４回繰り返す工程と、
（ｆ）工程（ｅ）の処理によって得られる陽極箔を６〜１２ｗｔ％塩酸、０．０５〜１ｗｔ％硫酸、０．０１〜１ｗｔ％りん酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．１〜１Ａ／ｃｍ2であり、温度が１０〜４５℃であり、正弦波として変わる５〜３５Ｈｚ電源周波数で１０〜８５秒低周波数でエッチングする工程と、
（ｇ）工程（ｆ）の処理によって得られる陽極箔を６〜１２ｗｔ％塩酸、０．０５〜１ｗｔ％硫酸、０．０１〜１ｗｔ％りん酸で、温度が１０〜４５℃である条件で１０〜８５秒処理する工程と、
（ｈ）工程（ｇ）で得られる陽極箔を温度が４０〜６０℃の水道水で１０〜８５秒洗浄する工程と、
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す工程と、
（ｊ）２〜６ｗｔ％の塩酸溶液で、温度が２０〜８０℃で３０〜１８０秒浸漬する工程と、
（ｋ）０．１〜４ｗｔ％の硝酸溶液で、温度が２０〜８０℃で３０〜１８０秒浸漬する工程と、
（ｌ）純水で３０〜１８０秒洗浄した後、４００〜４６０℃温度で２０〜１８０秒アニール処理する工程とを含む低接触抵抗の低圧用アルミニウム電解コンデンサ用の電極箔のエッチング方法という技術的手段によって実現される。
An object of the present invention is
(A) A step of immersing a low-pressure anode foil for an electrolytic capacitor in a 0.01 to 5 wt% sodium hydroxide solution at a temperature of 20 to 60 ° C. for 0.5 to 3 minutes.
(B) The anode foil obtained in step (a) is 6 to 12 wt% hydrochloric acid and 0.05 to 1 wt% sulfuric acid, the temperature is 5 to 50 ° C., and the current density is 0.1 to 1 A / cm 2 . The process of processing for 10 to 85 seconds under the conditions and
(C) A step of treating the anode foil obtained in step (b) with 6 to 12 wt% hydrochloric acid and 0.05 to 1 wt% sulfuric acid for 10 to 85 seconds under the condition that the temperature is 5 to 50 ° C.
(D) A step of washing the anode foil obtained in step (c) with tap water having a temperature of 40 to 60 ° C. for 10 to 85 seconds.
(E) Steps (b), (c,) (d) are repeated four times, and
(F) The anode foil obtained by the treatment of step (e) is etched with 6 to 12 wt% hydrochloric acid, 0.05 to 1 wt% sulfuric acid, and 0.01 to 1 wt% phosphoric acid etching solution to expand the holes, and the current density is increased. Etching at a low frequency of 10 to 85 seconds at a power supply frequency of 5 to 35 Hz, which changes as a sine wave, with a temperature of 0.1 to 1 A / cm 2 and a temperature of 10 to 45 ° C.
(G) The anode foil obtained by the treatment of step (f) is 6 to 12 wt% hydrochloric acid, 0.05 to 1 wt% sulfuric acid, 0.01 to 1 wt% phosphoric acid under the condition that the temperature is 10 to 45 ° C. ~ 85 seconds processing process and
(H) A step of washing the anode foil obtained in step (g) with tap water having a temperature of 40 to 60 ° C. for 10 to 85 seconds.
(I) A step of repeating steps (f), (g), and (h) eight times, and
(J) A step of immersing in a 2 to 6 wt% hydrochloric acid solution at a temperature of 20 to 80 ° C. for 30 to 180 seconds.
(K) A step of immersing in a 0.1 to 4 wt% nitric acid solution at a temperature of 20 to 80 ° C. for 30 to 180 seconds.
(L) A technical method of etching an electrode foil for a low-pressure aluminum electrolytic capacitor having low contact resistance, which includes a step of washing with pure water for 30 to 180 seconds and then annealing at a temperature of 400 to 460 ° C. for 20 to 180 seconds. It is realized by means.
本発明は、従来の技術と比べると、
アルカリ液前処理、穴あけ及び穴を拡げるプロセスが一つずつ行われ、各ステップ後に槽液での中間処理及び温水洗浄フローが増え、穴を拡げる際に、電源の周波数を制御することによって、均一な残芯層のエッチング形状を得て、低接触抵抗を得る低周波数でのエッチング方法が実現するというメリットを有する。
The present invention is compared with the prior art.
Alkaline solution pretreatment, drilling and hole expansion processes are performed one by one, and after each step, the intermediate treatment with tank solution and hot water cleaning flow increase, and when the holes are expanded, the frequency of the power supply is controlled to make it uniform. It has the merit of realizing an etching method at a low frequency to obtain a good etching shape of the residual core layer and obtain a low contact resistance.
以下、具体的な実施例を組み合わせて本発明を更に説明するが、本発明は、以下の実施例に限定されるものではない。特記しない限り、前記方法は常例の方法である。 Hereinafter, the present invention will be further described in combination with specific examples, but the present invention is not limited to the following examples. Unless otherwise specified, the method is a conventional method.
実施例１
（ａ）電解コンデンサ用の低圧用陽極箔を０．０１ｗｔ％の水酸化ナトリウム溶液に入れ、４０℃の温度で３分間浸漬する。
（ｂ）工程（ａ）で得られる陽極箔を６ｗｔ％塩酸、０．１ｗｔ％硫酸で、温度が３０℃であり、電流密度が０．３Ａ／ｃｍ2である条件で２０秒処理する。
（ｃ）工程（ｂ）で得られる陽極箔を６ｗｔ％塩酸、０．１ｗｔ％硫酸で、温度が３０℃の条件で２０秒処理する。
（ｄ）工程（ｃ）で得られる陽極箔を温度が４０℃の水道水で３０秒洗浄する。
（ｅ）工程（ｂ）、（ｃ）、（ｄ）を４回繰り返す。
（ｆ）工程（ｅ）の処理によって得られる陽極箔を６ｗｔ％塩酸、０．１ｗｔ％硫酸、０．０１ｗｔ％りん酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．１Ａ／ｃｍ2であり、温度が３０℃であり、正弦波として変わる５〜３５Ｈｚ周波数で低くから高くまで２０秒低周波数でエッチングする。
（ｇ）工程（ｆ）の処理によって得られる陽極箔を６ｗｔ％塩酸、０．１ｗｔ％硫酸、０．０１ｗｔ％りん酸で、温度が３０℃である条件で２０秒処理する。
（ｈ）工程（ｇ）で得られる陽極箔を采用温度が４０℃の水道水で３０秒洗浄する。
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す。
（ｊ）２ｗｔ％の塩酸溶液で、温度が５０℃で３０秒浸漬する。
（ｋ）０．１ｗｔ％の硝酸溶液で、温度が５０℃で３０秒浸漬する。
（ｌ）純水で６０秒洗浄した後、４２０℃の温度で１５０秒アニール処理する。
Example 1
(A) A low-voltage anode foil for an electrolytic capacitor is placed in a 0.01 wt% sodium hydroxide solution and immersed at a temperature of 40 ° C. for 3 minutes.
(B) The anode foil obtained in step (a) is treated with 6 wt% hydrochloric acid and 0.1 wt% sulfuric acid for 20 seconds under the conditions of a temperature of 30 ° C. and a current density of 0.3 A / cm 2 .
(C) The anode foil obtained in step (b) is treated with 6 wt% hydrochloric acid and 0.1 wt% sulfuric acid at a temperature of 30 ° C. for 20 seconds.
(D) The anode foil obtained in step (c) is washed with tap water having a temperature of 40 ° C. for 30 seconds.
(E) Steps (b), (c) and (d) are repeated four times.
(F) The anode foil obtained by the treatment of step (e) is etched with 6 wt% hydrochloric acid, 0.1 wt% sulfuric acid, and 0.01 wt% phosphoric acid etching solution to expand the holes, and the current density is 0.1 A / cm. Etching is performed at a low frequency of 20 seconds from low to high at a frequency of 5 to 35 Hz, which is 2 , the temperature is 30 ° C., and changes as a sine wave.
(G) The anode foil obtained by the treatment in step (f) is treated with 6 wt% hydrochloric acid, 0.1 wt% sulfuric acid, and 0.01 wt% phosphoric acid for 20 seconds under the condition that the temperature is 30 ° C.
(H) The anode foil obtained in step (g) is washed with tap water having a heating temperature of 40 ° C. for 30 seconds.
(I) Steps (f), (g) and (h) are repeated 8 times.
(J) Immerse in a 2 wt% hydrochloric acid solution at a temperature of 50 ° C. for 30 seconds.
(K) Immerse in 0.1 wt% nitric acid solution at a temperature of 50 ° C. for 30 seconds.
(L) After washing with pure water for 60 seconds, annealing treatment is performed at a temperature of 420 ° C. for 150 seconds.
実施例２
（ａ）電解コンデンサ用の低圧用陽極箔を０．５ｗｔ％の水酸化ナトリウム溶液に入れ、５０℃温度で２分間浸漬する。
（ｂ）工程（ａ）で得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸で、温度が４０℃で、電流密度が０．５Ａ／ｃｍ2である条件で４０秒処理する。
（ｃ）工程（ｂ）で得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸で、温度が４０℃である条件で４０秒処理する。
（ｄ）工程（ｃ）で得られる陽極箔を温度が４５℃の水道水で４０秒洗浄する。
（ｅ）工程（ｂ）、（ｃ）、（ｄ）を４回繰り返す。
（ｆ）工程（ｅ）の処理によって得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸、０．１ｗｔ％りん酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．３Ａ／ｃｍ2で、温度が３５℃で、正弦波として変わる５〜３５Ｈｚ周波数で低くから高くまで４０秒低周波数でエッチングする。
（ｇ）工程（ｆ）の処理によって得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸、０．１ｗｔ％りん酸で、温度が３５℃である条件で４０秒処理する。
（ｈ）工程（ｇ）で得られる陽極箔を温度が４５℃の水道水で４０秒洗浄する。
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す。
（ｊ）３ｗｔ％の塩酸溶液で、温度が６０℃で６０秒浸漬する。
（ｋ）１ｗｔ％の硝酸溶液で、温度が６０℃で６０秒浸漬する。
（ｌ）純水で９０秒洗浄した後、４３０℃温度で１２０秒アニール処理する。
Example 2
(A) A low-voltage anode foil for an electrolytic capacitor is placed in a 0.5 wt% sodium hydroxide solution and immersed at a temperature of 50 ° C. for 2 minutes.
(B) The anode foil obtained in step (a) is treated with 8 wt% hydrochloric acid and 0.3 wt% sulfuric acid for 40 seconds under the conditions of a temperature of 40 ° C. and a current density of 0.5 A / cm 2 .
(C) The anode foil obtained in step (b) is treated with 8 wt% hydrochloric acid and 0.3 wt% sulfuric acid for 40 seconds under the condition that the temperature is 40 ° C.
(D) The anode foil obtained in step (c) is washed with tap water having a temperature of 45 ° C. for 40 seconds.
(E) Steps (b), (c) and (d) are repeated four times.
(F) The anode foil obtained by the treatment of step (e) is etched with 8 wt% hydrochloric acid, 0.3 wt% sulfuric acid, and 0.1 wt% phosphoric acid etching solution to expand the holes, and the current density is 0.3 A / cm. At 2 , the temperature is 35 ° C., and etching is performed at a low frequency of 5 to 35 Hz, which changes as a sine wave, from low to high for 40 seconds.
(G) The anode foil obtained by the treatment in step (f) is treated with 8 wt% hydrochloric acid, 0.3 wt% sulfuric acid and 0.1 wt% phosphoric acid for 40 seconds under the condition that the temperature is 35 ° C.
(H) The anode foil obtained in step (g) is washed with tap water having a temperature of 45 ° C. for 40 seconds.
(I) Steps (f), (g) and (h) are repeated 8 times.
(J) Immerse in a 3 wt% hydrochloric acid solution at a temperature of 60 ° C. for 60 seconds.
(K) Immerse in 1 wt% nitric acid solution at a temperature of 60 ° C. for 60 seconds.
(L) After washing with pure water for 90 seconds, annealing treatment is performed at a temperature of 430 ° C. for 120 seconds.
実施例３
（ａ）電解コンデンサ用の低圧用陽極箔を２ｗｔ％の水酸化ナトリウム溶液に入れ、５５℃温度で１分間浸漬する。
（ｂ）工程（ａ）で得られる陽極箔を１０ｗｔ％塩酸、０．５ｗｔ％硫酸で、温度が４５℃、電流密度が０．７Ａ／ｃｍ2である条件で６０秒処理する。
（ｃ）工程（ｂ）で得られる陽極箔を１０ｗｔ％塩酸、０．５ｗｔ％硫酸で、温度が４５℃である条件で６０秒処理する。
（ｄ）工程（ｃ）で得られる陽極箔を温度が５０℃の水道水で６０秒洗浄する。
（ｅ）工程（ｂ）、（ｃ）、（ｄ）を４回繰り返す。
（ｆ）工程（ｅ）の処理によって得られる陽極箔を１０ｗｔ％塩酸、０．５ｗｔ％硫酸、０．５ｗｔ％りん酸エッチング液で穴を拡げるエッチングし、電流密度が０．４Ａ／ｃｍ2で、温度が４０℃で、正弦波として変わる５〜３５Ｈｚ周波数で低くから高くまで６０秒低周波数でエッチングする。
（ｇ）工程（ｆ）の処理によって得られる陽極箔を１０ｗｔ％塩酸、０．５ｗｔ％硫酸、０．５ｗｔ％りん酸で、温度が４０℃である条件で６０秒処理する。
（ｈ）工程（ｇ）で得られる陽極箔を温度が５０℃の水道水で６０秒洗浄する。
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す。
（ｊ）４ｗｔ％の塩酸溶液で、温度が７０℃で９０秒浸漬する。
（ｋ）２ｗｔ％の硝酸溶液で、温度が７０℃で９０秒浸漬する。
（ｌ）純水で１２０秒洗浄した後、４４０℃温度で９０秒アニール処理する。
Example 3
(A) A low-voltage anode foil for an electrolytic capacitor is placed in a 2 wt% sodium hydroxide solution and immersed at a temperature of 55 ° C. for 1 minute.
(B) The anode foil obtained in step (a) is treated with 10 wt% hydrochloric acid and 0.5 wt% sulfuric acid for 60 seconds under the conditions of a temperature of 45 ° C. and a current density of 0.7 A / cm 2 .
(C) The anode foil obtained in step (b) is treated with 10 wt% hydrochloric acid and 0.5 wt% sulfuric acid for 60 seconds under the condition that the temperature is 45 ° C.
(D) The anode foil obtained in step (c) is washed with tap water having a temperature of 50 ° C. for 60 seconds.
(E) Steps (b), (c) and (d) are repeated four times.
(F) The anode foil obtained by the treatment of step (e) is etched with 10 wt% hydrochloric acid, 0.5 wt% sulfuric acid, and 0.5 wt% phosphoric acid etching solution to widen the holes, and the current density is 0.4 A / cm 2 . Etching at a low frequency of 60 seconds from low to high at a frequency of 5 to 35 Hz, which changes as a sine wave at a temperature of 40 ° C.
(G) The anode foil obtained by the treatment in step (f) is treated with 10 wt% hydrochloric acid, 0.5 wt% sulfuric acid and 0.5 wt% phosphoric acid for 60 seconds under the condition that the temperature is 40 ° C.
(H) The anode foil obtained in step (g) is washed with tap water having a temperature of 50 ° C. for 60 seconds.
(I) Steps (f), (g) and (h) are repeated 8 times.
(J) Immerse in 4 wt% hydrochloric acid solution at a temperature of 70 ° C. for 90 seconds.
(K) Immerse in a 2 wt% nitric acid solution at a temperature of 70 ° C. for 90 seconds.
(L) After washing with pure water for 120 seconds, annealing treatment is performed at a temperature of 440 ° C. for 90 seconds.
実施例４
（ａ）４ｗｔ％の水酸化ナトリウム溶液で、６０℃温度で電解コンデンサ用の低圧用陽極箔を０．５分間浸漬する。
（ｂ）工程（ａ）で得られる陽極箔を１２ｗｔ％塩酸、０．８ｗｔ％硫酸で、温度が５０℃、電流密度が０．９Ａ／ｃｍ2である条件で８０秒処理する。
（ｃ）工程（ｂ）で得られる陽極箔を１２ｗｔ％塩酸、０．８ｗｔ％硫酸で、温度が５０℃である条件で８０秒処理する。
（ｄ）工程（ｃ）で得られる陽極箔を温度が５５℃の水道水で４０秒洗浄する。
（ｅ）工程（ｂ）、（ｃ）、（ｄ）を４回繰り返す。
（ｆ）工程（ｅ）の処理によって得られる陽極箔を１２ｗｔ％塩酸、０．８ｗｔ％硫酸、０．８ｗｔ％りん酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．５Ａ／ｃｍ2で、温度が４５℃で、正弦波として変わる５〜３５Ｈｚ周波数で低くから高くまで８０秒低周波数でエッチングする。
（ｇ）工程（ｆ）の処理によって得られる陽極箔を１２ｗｔ％塩酸、０．８ｗｔ％硫酸、０．８ｗｔ％りん酸で、温度が４５℃である条件で８０秒処理する。
（ｈ）工程（ｇ）で得られる陽極箔を温度が８０℃の水道水で４０秒洗浄する。
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す。
（ｊ）５ｗｔ％の塩酸溶液で、温度が８０℃で１２０秒浸漬する。
（ｋ）３ｗｔ％の硝酸溶液で、温度が５５℃で１２０秒浸漬する。
（ｌ）純水で１５０秒洗浄した後、４５０℃温度で６０秒アニール処理する。
Example 4
(A) Immerse a low-pressure anode foil for an electrolytic capacitor in a 4 wt% sodium hydroxide solution at a temperature of 60 ° C. for 0.5 minutes.
(B) The anode foil obtained in step (a) is treated with 12 wt% hydrochloric acid and 0.8 wt% sulfuric acid for 80 seconds under the conditions of a temperature of 50 ° C. and a current density of 0.9 A / cm 2 .
(C) The anode foil obtained in step (b) is treated with 12 wt% hydrochloric acid and 0.8 wt% sulfuric acid for 80 seconds under the condition that the temperature is 50 ° C.
(D) The anode foil obtained in step (c) is washed with tap water having a temperature of 55 ° C. for 40 seconds.
(E) Steps (b), (c) and (d) are repeated four times.
(F) The anode foil obtained by the treatment of step (e) is etched with 12 wt% hydrochloric acid, 0.8 wt% sulfuric acid, and 0.8 wt% phosphoric acid etching solution to expand the holes, and the current density is 0.5 A / cm. At 2 , the temperature is 45 ° C., and etching is performed at a low frequency of 5 to 35 Hz, which changes as a sine wave, from low to high for 80 seconds.
(G) The anode foil obtained by the treatment in step (f) is treated with 12 wt% hydrochloric acid, 0.8 wt% sulfuric acid and 0.8 wt% phosphoric acid for 80 seconds under the condition that the temperature is 45 ° C.
(H) The anode foil obtained in step (g) is washed with tap water having a temperature of 80 ° C. for 40 seconds.
(I) Steps (f), (g) and (h) are repeated 8 times.
(J) Immerse in 5 wt% hydrochloric acid solution at a temperature of 80 ° C. for 120 seconds.
(K) Immerse in a 3 wt% nitric acid solution at a temperature of 55 ° C. for 120 seconds.
(L) After washing with pure water for 150 seconds, annealing treatment is performed at a temperature of 450 ° C. for 60 seconds.
比較例（従来のエッチングプロセス）
（ａ）０．０５ｗｔ％のりん酸溶液で、６０℃温度で電解コンデンサ用の低圧用陽極箔を１分間浸漬する。
（ｂ）工程（ａ）で得られる陽極箔を８ｗｔ％塩酸、０．５ｗｔ％硫酸で、温度が５０℃、電流密度が０．３Ａ／ｃｍ2である条件で３分間処理する。
（ｃ）工程（ｂ）の処理によって得られる陽極箔を８ｗｔ％塩酸、０．５ｗｔ％硫酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．３Ａ／ｃｍ2で、温度が５０℃で、正弦波として変わる５０Ｈｚ電源周波数で４分間電気化学エッチングする。
（ｄ）工程（ｃ）の処理によって得られる陽極箔を１ｗｔ％の硝酸溶液で、温度が７０℃で６０秒浸漬する。
（ｅ）純水で６０秒洗浄した後、４２０℃温度で６０秒アニール処理する。
Comparative example (conventional etching process)
(A) A low-pressure anode foil for an electrolytic capacitor is immersed in a 0.05 wt% phosphoric acid solution at a temperature of 60 ° C. for 1 minute.
(B) The anode foil obtained in step (a) is treated with 8 wt% hydrochloric acid and 0.5 wt% sulfuric acid for 3 minutes under the conditions of a temperature of 50 ° C. and a current density of 0.3 A / cm 2 .
(C) The anode foil obtained by the treatment of step (b) is etched with 8 wt% hydrochloric acid and 0.5 wt% sulfuric acid etching solution to expand holes, and the current density is 0.3 A / cm 2 and the temperature is 50 ° C. Then, electrochemical etching is performed for 4 minutes at a 50 Hz power supply frequency that changes as a sine wave.
(D) The anode foil obtained by the treatment of step (c) is immersed in a 1 wt% nitric acid solution at a temperature of 70 ° C. for 60 seconds.
(E) After washing with pure water for 60 seconds, annealing treatment is performed at a temperature of 420 ° C. for 60 seconds.
本発明によるエッチング電極箔を、従来のプロセスによるエッチング電極箔が生産ラインで化成された後、対比したデータの結果は以下の通りである（化成条件：アジピン酸アンモニウム槽液、Ｖｆｅ＝２１Ｖ）。 The results of data comparing the etching electrode foil according to the present invention after the etching electrode foil by the conventional process was formed on the production line are as follows (chemical conditions: ammonium adipate bath solution, Vfe = 21V).
対比結果から、本発明エッチングプロセスによるエッチング電極箔は化成後、接触抵抗が顕著に低下し、従来のエッチングプロセスに比べると、４０％を超えて低下することがわかる。 From the comparison results, it can be seen that the contact resistance of the etching electrode foil obtained by the etching process of the present invention is remarkably reduced after chemical conversion, which is more than 40% lower than that of the conventional etching process.
本発明は、アルカリ液前処理、穴あけ及び穴を拡げるプロセスを一つずつ行い、各ステップ後に槽液による中間処理及び温水洗浄フローが増えることによって、穴を拡げる際に、電源周波数を制御することによって、均一な残芯層エッチング形状を得る。 According to the present invention, the process of pretreatment with an alkaline solution, drilling, and expanding a hole is performed one by one, and after each step, the intermediate treatment with the tank solution and the hot water cleaning flow are increased to control the power supply frequency when expanding the hole. To obtain a uniform residual core layer etching shape.
出願人は又、本発明は上記実施例によって本発明の実現方法及び装置構造を説明するが、本発明は上記実施形態に限定されず、即ち、本発明は上記方法及び構造によって実現されなければならないことを意味しない。所属技術分野の技術者は、本発明に対するいかなる改善、本発明に用いられる実現方法の及び工程に対する添加、実施形態の選択等がいずれも本発明の保護範囲と開示の範囲内に落ちることがわかるべきである。 The applicant also describes the method and device structure of the present invention according to the above examples, but the present invention is not limited to the above embodiments, that is, the present invention must be realized by the above methods and structures. It doesn't mean that it doesn't become. Engineers in the technical field to which they belong find that any improvements to the present invention, additions to the implementation methods and processes used in the present invention, selection of embodiments, etc. fall within the scope of protection and disclosure of the present invention. Should be.
本発明は、上記実施形態に限定されず、本発明と近似する構造及びその方法によって本発明の目的を実現する全ての手段はいずれも本発明の保護範囲内にある。 The present invention is not limited to the above-described embodiment, and all means for realizing the object of the present invention by a structure similar to the present invention and a method thereof are within the protection scope of the present invention.
Claims (1)
（ｂ）工程（ａ）で得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸で、温度が４０℃であり、電流密度が０．５Ａ／ｃｍ2である条件で４０秒処理する工程と、
（ｃ）工程（ｂ）で得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸で、温度が４０℃である条件で４０秒処理する工程と、
（ｄ）工程（ｃ）で得られる陽極箔を温度が４５℃の水道水で４０秒洗浄する工程と、
（ｅ）工程（ｂ）、（ｃ、）、（ｄ）を４回繰り返す工程と、
（ｆ）工程（ｅ）の処理によって得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸、０．１ｗｔ％りん酸エッチング液で穴を拡げるためにエッチングし、電流密度が０．３Ａ／ｃｍ2であり、温度が３５℃であり、正弦波として変わる５〜３５Ｈｚ電源周波数で４０秒低周波数でエッチングする工程と、
（ｇ）工程（ｆ）の処理によって得られる陽極箔を８ｗｔ％塩酸、０．３ｗｔ％硫酸、０．１ｗｔ％りん酸で、温度が３５℃である条件で４０秒処理する工程と、
（ｈ）工程（ｇ）で得られる陽極箔を温度が４５℃の水道水で４０秒洗浄する工程と、
（ｉ）工程（ｆ）、（ｇ）、（ｈ）を８回繰り返す工程と、
（ｊ）３ｗｔ％の塩酸溶液で、温度が６０℃で６０秒浸漬する工程と、
（ｋ）１ｗｔ％の硝酸溶液で、温度が６０℃で６０秒浸漬する工程と、
（ｌ）純水で３０〜１８０秒洗浄した後、４３０℃温度で１２０秒アニール処理する工程とを含み、工程（ｂ）、（ｃ）、（ｇ）におけるエッチング処理の電源としては直流、交流、直流交流交互使用のうちいずれか1項であることを特徴とする低接触抵抗の低圧用アルミニウム電解コンデンサ用の電極箔のエッチング方法。 (A) A step of immersing a low-voltage anode foil for an electrolytic capacitor in a 0.5 wt% sodium hydroxide solution at a temperature of 50 ° C. for 2 minutes.
(B) The anode foil obtained in step (a) is treated with 8 wt% hydrochloric acid and 0.3 wt% sulfuric acid for 40 seconds under the conditions of a temperature of 40 ° C. and a current density of 0.5 A / cm 2. And the process to do
(C) A step of treating the anode foil obtained in step (b) with 8 wt% hydrochloric acid and 0.3 wt% sulfuric acid for 40 seconds under the condition that the temperature is 40 ° C.
(D) A step of washing the anode foil obtained in step (c) with tap water having a temperature of 45 ° C. for 40 seconds, and
(E) A step of repeating steps (b), (c,), and (d) four times, and
(F) The anode foil obtained by the treatment of step (e) is etched with 8 wt% hydrochloric acid, 0.3 wt% sulfuric acid, and 0.1 wt% phosphoric acid etching solution to expand the holes, and the current density is 0. 3 A / cm 2 , the temperature is 35 ° C, and the process of etching at a low frequency of 5 to 35 Hz, which changes as a sine wave, for 40 seconds.
(G) A step of treating the anode foil obtained by the treatment of step (f) with 8 wt% hydrochloric acid, 0.3 wt% sulfuric acid, and 0.1 wt% phosphoric acid for 40 seconds under the condition that the temperature is 35 ° C. ,
(H) A step of washing the anode foil obtained in step (g) with tap water having a temperature of 45 ° C. for 40 seconds, and
(I) A step of repeating steps (f), (g), and (h) eight times, and
(J) A step of immersing in a 3 wt% hydrochloric acid solution at a temperature of 60 ° C. for 60 seconds, and
(K) A step of immersing in a 1 wt% nitric acid solution at a temperature of 60 ° C. for 60 seconds, and
(L) After washing 180 seconds with pure water, saw including a step of 120 seconds annealing at 430 ° C. temperature, step (b), (c), direct current as a power source for an etching process in (g), A method for etching an electrode foil for a low-voltage aluminum electrolytic capacitor with low contact resistance, which is characterized by one of alternating current and direct current alternating current .
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| CN108486645B (en) * | 2018-03-19 | 2020-09-22 | 南通海星电子股份有限公司 | Corrosion method of low-voltage electrode foil of surface mount type aluminum electrolytic capacitor |
| CN112981516B (en) * | 2021-02-03 | 2022-04-05 | 广州金立电子有限公司 | Anode aluminum foil corrosion method for aluminum electrolytic capacitor |
| CN113026087B (en) * | 2021-04-29 | 2021-08-10 | 南通海星电子股份有限公司 | Preparation method of nano-microporous structure aluminum electrode foil for automobile electronics |
| CN113279046A (en) * | 2021-05-20 | 2021-08-20 | 浙江丰川电子环保科技股份有限公司 | Rapid chemical corrosion process for anode aluminum foil for electrolytic capacitor |
| CN113611536A (en) * | 2021-08-10 | 2021-11-05 | 南通海星电子股份有限公司 | Manufacturing method for reducing foil dust of low-voltage electrode foil |
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